CN102947343A - Manufacturing of microcellulose - Google Patents
Manufacturing of microcellulose Download PDFInfo
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- CN102947343A CN102947343A CN2011800280416A CN201180028041A CN102947343A CN 102947343 A CN102947343 A CN 102947343A CN 2011800280416 A CN2011800280416 A CN 2011800280416A CN 201180028041 A CN201180028041 A CN 201180028041A CN 102947343 A CN102947343 A CN 102947343A
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- cellulose
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- hydrolysis
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- 238000004519 manufacturing process Methods 0.000 title description 12
- 239000000463 material Substances 0.000 claims abstract description 64
- 229920002678 cellulose Polymers 0.000 claims abstract description 63
- 239000001913 cellulose Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 40
- 238000005406 washing Methods 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 3
- 235000010980 cellulose Nutrition 0.000 claims description 61
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 34
- 235000019813 microcrystalline cellulose Nutrition 0.000 claims description 34
- 230000007062 hydrolysis Effects 0.000 claims description 33
- 238000006460 hydrolysis reaction Methods 0.000 claims description 33
- 239000008108 microcrystalline cellulose Substances 0.000 claims description 33
- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 33
- 229920001131 Pulp (paper) Polymers 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000009826 distribution Methods 0.000 claims description 10
- 230000020477 pH reduction Effects 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000018044 dehydration Effects 0.000 claims description 8
- 238000006297 dehydration reaction Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000004061 bleaching Methods 0.000 claims description 7
- 229920000742 Cotton Polymers 0.000 claims description 5
- 235000013339 cereals Nutrition 0.000 claims description 5
- 244000025254 Cannabis sativa Species 0.000 claims description 4
- 229920000875 Dissolving pulp Polymers 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 4
- 244000299507 Gossypium hirsutum Species 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 229920005610 lignin Polymers 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- JXAZAUKOWVKTLO-UHFFFAOYSA-L sodium pyrosulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OS([O-])(=O)=O JXAZAUKOWVKTLO-UHFFFAOYSA-L 0.000 claims description 3
- 239000011122 softwood Substances 0.000 claims description 3
- 244000198134 Agave sisalana Species 0.000 claims description 2
- 235000011624 Agave sisalana Nutrition 0.000 claims description 2
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 2
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 2
- 241000196324 Embryophyta Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 240000000907 Musa textilis Species 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 235000009120 camo Nutrition 0.000 claims description 2
- 235000005607 chanvre indien Nutrition 0.000 claims description 2
- 239000011121 hardwood Substances 0.000 claims description 2
- 239000011487 hemp Substances 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000004537 pulping Methods 0.000 claims description 2
- 239000005031 sulfite paper Substances 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229920002488 Hemicellulose Polymers 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 230000006835 compression Effects 0.000 description 5
- 238000007906 compression Methods 0.000 description 5
- 238000010411 cooking Methods 0.000 description 5
- 238000012676 equilibrium polymerization Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005903 acid hydrolysis reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000413 hydrolysate Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000012511 carbohydrate analysis Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- -1 makeup Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000006140 methanolysis reaction Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- 239000001814 pectin Substances 0.000 description 2
- 229920001277 pectin Polymers 0.000 description 2
- 235000010987 pectin Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000005418 vegetable material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 241000186514 Warburgia ugandensis Species 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010902 jet-milling Methods 0.000 description 1
- 239000012978 lignocellulosic material Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000012254 magnesium hydroxide Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 238000003921 particle size analysis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001507 sample dispersion Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H8/00—Macromolecular compounds derived from lignocellulosic materials
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Paper (AREA)
Abstract
The present invention relates to a process for producing microcellulose comprising a) acidifying fibrous cellulosic material, b) washing the acidified cellulosic material, c) optionally dewatering the washed cellulosic material, and d) hydrolyzing the washed or washed and dewatered cellulosic material under acidic conditions at a temperature of at least 120 DEG C and at a consistency of at least 8% on dry weight of the cellulose.
Description
Invention field
The present invention relates to be prepared by fibrous cellulosic materials the method for Microcrystalline Cellulose, the method comprises acidification step and hydrolysing step.
Background of invention
Microcrystalline Cellulose (being also referred to as the Mierocrystalline cellulose and the avicel cellulose that for example reach equilibrium polymerization degree (Level-off DP)) is the universal product in food, medicine, makeup, paper and cardboard and many other application for example in many industrial application.Microcrystalline Cellulose also can be used for producing the derivative of Microcrystalline Cellulose, for example prezenta, CMC, nano-cellulose and various composite prod.
Some methods for the production of Microcrystalline Cellulose have been proposed in patent documentation.
US 2978446 has described the Mierocrystalline cellulose that reaches equilibrium polymerization degree (DP, degree of polymerization) by acid hydrolysis and mechanical treatment production.Utilization is boiled in 2.5 nominal hydrochloric acid (HCl) and is made cellulose hydrolysis.Therefore acid concentration is 9%, and temperature is approximately 105 ℃.Do not stipulate the concentration of paper pulp and the amount of add of acid.The Mierocrystalline cellulose of hydrolysis need to be in aqueous medium mechanical depolymerization.
US 3278519 has described by making cellulose hydrolysis production reach the cellulosic similar approach of equilibrium polymerization degree with 2.5 nominal HCl or under 250 °F (121 ℃) with 0.5%HCl under 105 ℃.Do not stipulate the concentration of paper pulp and the amount of add of acid.
US 3954727 discloses by making cellulose hydrolysis produce the method for avicel cellulose with dilute sulphuric acid under 120-160 ℃ temperature.Mierocrystalline cellulose is joined wherein dilute sulphuric acid to have 1% concentration and Mierocrystalline cellulose-acid substance and has 5% concentration.Therefore, the concentration of paper pulp is low and high based on the amount of the acid of Mierocrystalline cellulose dry weight basis.
US 7037405 has described a kind of method, former paper pulp material contact with acid and heats under the temperature that improves and then carries out mechanical treatment.The suitable acid concentration of mentioning is the 1-5% of mixture, and suitable pulp density is 3-50%, and suitable temperature range is 80-120 ℃, and the suitable reaction times is 30 minutes-4 hours.After acid hydrolysis, pulp mixture is carried out mechanical treatment so that the fiber depolymerization.Preferably, the mechanical depolymerization treatment step cuts into the approximately micron size of 1-10 micron-scale with the crystalline fibers crude granule.The method of US 7037405 is subjected to complicated production technique.After acid hydrolysis, need the mechanical depolymerization step.Should the stage need the correct grinding unit of high cost and the correct grinding energy of 5-100kWh/ ton aborning.
US 6228213 discloses by acid solution being joined in the Mierocrystalline cellulose and with Mierocrystalline cellulose and acid solution and has fed the method for producing avicel cellulose by forcing machine, wherein makes described Mierocrystalline cellulose stand acid hydrolysis and forms avicel cellulose.The temperature of extruder barrel is 80-200 ℃ during being hydrolyzed.Because the pressure that the temperature of forcing machine and the die head of forcing machine or screw rod produce, Mierocrystalline cellulose is melting in forcing machine, and this allows to carry out closer contact between Mierocrystalline cellulose and the acid.The compression ratio of extruder screw is 1.5:1 and 3:1, preferred approximately 3:1.The shortcoming of forcing machine is their costlinesses, and maintenance cost is quite high, and the mechanical energy input that they need to be high, by being estimated as at least 100kWh of dried fibres element per ton, except typically the 150kWh(heat energy is inputted at least).
US 5543511 has described at the 100-200 ℃ of lower Mierocrystalline cellulose that reaches the equilibrium polymerization degree with oxygen and/or carbonic acid gas use partial hydrolysis production.
US 4427778 has described the Mierocrystalline cellulose that reaches the equilibrium polymerization degree by enzymic hydrolysis production.
In view of above-mentioned method for the production of Microcrystalline Cellulose, exist to produce Microcrystalline Cellulose in addition the needs of the method for efficient and cost-effective more.
Summary of the invention
According to the present invention, find that unexpectedly the high-quality Microcrystalline Cellulose with narrow size distribution can be produced by the following method by fibrous cellulosic materials: at first with the fibrous cellulosic materials acidifying, then wash the cellulose materials of this acidifying, make at last the cellulosic material hydrolysis of this washing.Size distribution can easily be controlled by the condition that changes acidification step and hydrolysing step.
Accompanying drawing is briefly described
Fig. 1 has shown the grain size distribution curve of Microcrystalline Cellulose produced according to the invention under the hydrolysis time of 165 ℃ hydrolysis temperature and 180 minutes, and
Fig. 2 has shown the grain size distribution curve of Microcrystalline Cellulose produced according to the invention under the hydrolysis time of 150 ℃ hydrolysis temperature and 120 minutes
Detailed Description Of The Invention
According to the invention provides the method for producing Microcrystalline Cellulose, the method comprises:
A) with the fibrous cellulosic materials acidifying,
B) wash the cellulose materials of this acidifying,
C) the cellulose materials dehydration that randomly will wash, and
D) with at least 120 ℃ temperature with at least 8% concentration of pressing the Mierocrystalline cellulose dry weight basis, under acidic conditions, make the cellulosic material hydrolysis of this washing or washing and dehydration.
The term that uses in this specification sheets " Microcrystalline Cellulose " comprises avicel cellulose MCC, but also refers to imperfect crystal but can contain the similar product in some amorphous territories.Microcrystalline Cellulose of the present invention typically has approximately 0-15 % by weight, preferred 0-10 % by weight, more preferably 0.5-7 % by weight, the hemicellulose level of 1-5% weight most preferably, described content records by typical carbohydrate analysis method (Determination of hemicelluloses and pectins in wood and pulp fibres by acid methanolysis and gas chromatography.1996.Nordic pulp and paper research journal nro 4,1996.216-219 page or leaf).
The present invention is based on such discovery: the cellulosic fibre of having removed metal becomes acidity, and this acidity is enough to keep (sustain) automatic hydrolysis, wherein utilizes the own acidity of cellulosic fibre.Cellulosic fibre contains the acidic-group that is attached to fibre wall, for example the ionogen of uronic acid and xylogen institute combination.During fiber contains usually and the metal ion of fiber acidity, for example Na
+, Ca
2+, Mg
2+And Mn
2+According to the present invention, remove metal by acidifying and washing from fiber.As the result of this ion exchange treatment, metal removed from fiber and fibre wall ionogen by protonated.For monovalent ion, ion-exchange can be described as follows usually:
Fiber-acid (-) Me
+→ fiber-acid (H)
For divalent-metal ion, ion-exchange can be described as usually:
2[fiber-acid (-)] Me
2+→ 2[fiber-acid (H)]
As the result of this ion-exchange, fiber (being the cell walls of fiber) becomes acidity, and this acidity is enough to keep automatic hydrolysis.The gained hydrolysed mix contains Microcrystalline Cellulose and comes from the reaction product of fiber, and non-metallic ion and salt, this is so that the further processing of Microcrystalline Cellulose is comparatively easy.
Acidification step a) in, preferably cellulose materials is acidified to 4 or be lower than 4, more preferably 3 or be lower than 3 pH value.This pH be preferably 0 or surpass 0, more preferably 0.5 or surpass 0.5, also more preferably 1 or surpass 1.This pH is preferably 0.5-4, more preferably 1-3, most preferably 1.5-2.5.
Acidification step a) in, the pKa value preferably than the acidic-group of cellulosic fibre for example uronic acid and the pKa value that is bonded to the ionogen of xylogen hang down at least 1, preferably at least 1.5, more preferably at least 2 units.
The suitable acid that is used for acidification step is mineral acid, for example sulfuric acid, hydrochloric acid, nitric acid, sodium pyrosulfate or sodium bisulfite.Can also use two or more the mixture in these acid.Preferred mineral acid is sulfuric acid.Can also use organic acid, for example formic acid.
The concentration of cellulose materials is preferably 5-40% with the cellulose materials dry weight basis in the acidification step, more preferably 10-30%.
Temperature in the acidification step is preferably less than 120 ℃, and more preferably 10-90 ℃, most preferably 20-70 ℃.
The residence time in the acidification step is preferably 10-90 minute, more preferably 15-60 minute.
After acidifying, the cellulose materials of acidifying is washed and chooses wantonly dehydration.Washing is preferably undertaken by following: make the cellulose materials of acidifying dewater to remove excessive acid, then dilute the cellulose materials of this dehydration and and then make this material dehydration.Described washing procedure can repeat once or twice.Cellulose materials with washing is diluted to aimed concn at last.
Washing can be undertaken by the industrial pulp washing device that utilization is generally used for the pulp mill machine.Preferred embodiment is included in carries out acidifying in the container, then remove disacidify by screw extruding, follows dilute with water, and again dewaters.
Provide as mentioned, in hydrolysis, utilize the own acidity of cellulose materials.And nonessential acid is joined in the hydrolysing step therefore.Yet, can be with a small amount of based on the Mierocrystalline cellulose dry weight basis, preferred maximum 0.5%, more preferably maximum 0.2%, most preferably maximum 0.18% acid joins in the hydrolysis.
Hydrolysis temperature is preferably 120-185 ℃, and more preferably 150-180 ℃, most preferably 155-175 ℃.
The concentration of cellulose materials is preferably 8-60% with the Mierocrystalline cellulose dry weight basis during being hydrolyzed, more preferably 10-50%, even more preferably 15-50%, most preferably 20-45%.
Hydrolysis time is preferably 20-300 minute, and more preferably 30-240 minute, also more preferably 60-240 minute, most preferably 60-240 minute.
Preferably, hydrolysis is in the situation that carrying out in very large (essential) compression not in the reactor, and the compression ratio of reactor preferably is lower than 1.5:1, more preferably less than 1.2:1.Preferably, during being hydrolyzed, provide mechanical energy input to guarantee uniform chemical substance and temperature distribution and do not have the very great machinery cutting of cellulose matrix to separate with mechanical fiber.
After hydrolysis, if necessary, the Microcrystalline Cellulose-hydrolysate admixture that obtains can neutralize or Microcrystalline Cellulose can be separated with hydrolysate.The Microcrystalline Cellulose that separates can be washed and Microcrystalline Cellulose that separate or washing can be neutralized.Can also the neutralizing acid hydrolysate.Can example such as yellow soda ash, sodium bicarbonate, potassium hydroxide, magnesium hydroxide or sodium hydroxide neutralize.Hydrolysate is rich in the hydrolysis of hemicellulose product, xylose and glucose for example, and can be for the production of ethanol.
Observe, by this specification sheets after a while the median size of described program determination be about 8-100 μ m, the microcrystalline cellulose cellulosic material of preferred 10-60 μ m, can be produced by the following method by fibrous cellulosic materials: acidifying fibrous cellulosic materials at first, then wash the cellulose materials of this acidifying, make at last the cellulosic material hydrolysis of this washing and subsequently depolymerization step not.Key character of the present invention is the high density of cellulose materials in the hydrolysis, and it is preferably at least 20% with the Mierocrystalline cellulose dry weight basis.High density has improved the concentration of chemical substance, and this has Beneficial Effect to speed of response, and so that easier from reaction mixture recovery Microcrystalline Cellulose.In addition, adding heat request can be lower.
Fibrous cellulosic materials as parent material can be any cellulose materials that can be hydrolyzed under prescribed condition in the methods of the invention.Fibrous cellulosic materials is also nonessential to be the pure cellulose material, but it also can contain for example xylogen of other material.
It is maximum 5% that the content of lignin of fibrous cellulose parent material is preferably, more preferably maximum 2%, and most preferably maximum 1%.
The fibrous cellulose parent material typically has approximately 3-15 % by weight, the hemicellulose level of preferred 5-10 % by weight, described content records by typical carbohydrate analysis method (Determination of hemicelluloses and pectins in wood and pulp fibres by acid methanolysis and gas chromatography.1996.Nordic pulp and paper research journal nro 4,1996.216-219 page or leaf).
The staple length of fibrous cellulose raw material is preferably 5-0.2mm.For non-wood fiber shape cellulose materials, cotton for example, staple length can be greater than 5mm.
Fibrous cellulosic materials can derive from the xylophyta material, for example soft wood or hardwood.
Preferred fibrous cellulosic materials is bleaching or unbleached dissolving pulp, for example sulfate pulping, soda-AQ paper pulp, sulfite pulp, neutral sulfite pulp, acid accumulator sulfite paper pulp or organic solvent paper pulp.Paper pulp can be softwood pulp or bardwood pulp.Paper pulp can be the paper pulp that obtains immediately after the boiling or after boiling the paper pulp of delignification or the paper pulp of delignification and bleaching.The paper pulp of preferred delignification is O
2The paper pulp of delignification.Preferred paper pulp is the paper pulp of full bleaching.
Also can use according to the present invention and to derive from for example fibrous cellulosic materials of stalk, flax, hemp, sisal hemp, abaca or the bamboo of cotton, grass, bagasse, cereal crop of non-woody lignocellulosic plants material.Usually with these vegetable materials of alkaline matter for processing ligno-cellulosic materials is broken to Mierocrystalline cellulose, xylogen and hemicellulose, then go out Mierocrystalline cellulose from described mixture separation.The vegetable material of some poor xylogen, for example velveteen or cotton fabric are not to necessarily require to process with alkaline matter.Rear kind of material can contain the fibrous material that has greater than 90% cotton fiber.
Fibrous cellulosic materials, for example dissolving pulp preferably have be lower than 40 Kappa numbers, more preferably less than 30 Kappa numbers, most preferably be lower than the content of lignin of 10 Kappa numbers.
According to the preferred embodiments of the invention, the Microcrystalline Cellulose of producing has narrow size distribution, wherein median size (D50) is 10-60 μ m, and preferably size distribution (D90) is so that the particle of at least 90 volume % has the size that is lower than 250 μ m.Particle diameter by this specification sheets after a while described program measure, described program comprises the supersound process that may cause sample depolymerization (deagglomerization) or decompose (disintegration).
The microcrystalline cellulose cellulosic material that obtains by the inventive method typically has in without any the mechanical treatment situation by this specification sheets 8-100 μ m of described program determination after a while, the median size of preferred 10-60 μ m.If need thinner particle diameter, but the described structure of refinement then.Therefore, can (if necessary) pass through to use suitable device, for example the rubbing device microcrystalline cellulose cellulosic material that will derive from hydrolysis is refined as less particle diameter, and wherein said refinement realizes by grinding stone (for example Masuko mill), high-shear mixer or jet milled machine.
The purity that a benefit of the inventive method is final Microcrystalline Cellulose is appropriate high and product can easily wash to remove low-molecular-weight carbohydrate.Through the Mierocrystalline cellulose purity of the Microcrystalline Cellulose of washing even can surpass 97%.
The yield of Microcrystalline Cellulose depends on processing condition, for example temperature, the amount of acid and the residence time and the concentration of acidifying and hydrolysis.Typical yield is at least 80%, preferably at least 85%, and yield even can be 90% or higher.
According to the present invention, Microcrystalline Cellulose can be produced in any suitable equipment (for example being equipped with the container of mixing tank or screw rod conveyor) that Mierocrystalline cellulose-acid mixture is not carried out therein any very large (substantial) compression.The latter can be the M ﹠amp with screw rod conveyor; The device of D pulp digester type.Other device can be continuous bleaching reactor or downflow system continuous steamer, for example pulp digester of Kamyr type.Compression ratio (if any) typically is lower than 1.5:1, more preferably less than 1.2:1.
Experimental section
Following examples have been described the operation of Microcrystalline Cellulose produced according to the invention.
In the 5L pulp digester that stirs with the mixing tank that passes lid, carry out the boiling experiment.Pulp digester is used in around the oil that flows in the chuck of this pulp digester and heats.Turning oil electricity consumption in independent unit is heated.
All boiling experiments are all undertaken by following mode.The cellulose materials that 300g is calculated by self dry weight (owen dry), namely paper pulp or other carry out depolymerization according to SCAN C 18:65, and dehydration is to 35% concentration in spin drier.Then with deionized water this paper pulp is diluted to 10% concentration and uses sulfuric acid (H
2SO
4) with pH regulator to 2.At room temperature kept this slurry 30 minutes.Thereafter with this pulp suspension Rotary drying to about 35% concentration to remove excessive acid.With deionized water by this paper pulp of following washing: at first it is diluted to 10% concentration and then with its Rotary drying to about 35% concentration.The repeated washing operation.Then with deionized water with this paper pulp redilution to aimed concn and transfer to autoclave for hydrolysis stage.Rate of heating with 2 ℃/min is heated to temperature of reaction until reach the goal response temperature with autoclave from room temperature.Therefore for example be heated to 150 ℃ of costs 65 minutes, be heated to 165 ℃ of costs 72.5 minutes.When reaching the goal response temperature, cooking time begins.During whole cooking time, make temperature remain in target temperature value.When cooking time is finished, by cooling off this autoclave unit with cold water (approximately 10 ℃ of temperature) refrigeration cycle oil.The cooling of reactor spends approximately 20 minutes.
Open the autoclave unit of cooling and cellulose mixtures shifted out and in the sack of being made by the cloth with 40 μ m holes (silk cloth), wash.For washing, use the 6000ml deionized water.
The particle diameter of cellulose product is by making with Mastersizer 2000(Ma Erwen (Malvern) the Instruments Ltd that is equipped with wetting dispersal unit Hydro 2000MU) measure with laser diffraction.Measure according to following operation:
With the cellulose materials sample dispersion in 500ml distilled water.Regulate sample concentration take degree of haze (obscuration) as 10% mode.Pump/the stirring velocity of dispersal unit is adjusted to 1500rpm.Before grain diameter measurement, sample is used supersound process 60 seconds.Measured particle diameter by 60 second timed interval with 3 continuously measureds.Calculate the mean value of 3 observed values.Each background value of measuring before sample.The Measuring Time that is used for each background and each sample measurement value is 5 seconds.Use the Fraunhofer parameter to measure.At Master sizer 2000application note MRK 561 (Wet method development for laser diffraction measurements) by Malvern Instruments and ISO-13320-1 (1:1999), provide the additional information about the laser diffraction measurement principle among the Particle size analysis – Laser diffraction General Principles.
With above-mentioned experiment processes employ in the paper pulp of full bleaching.The concentration of hydrolysis stage is 15%, and boiling temperature is 165 ℃, and cooking time is 180 minutes.The size distribution that in Fig. 1, has shown the Microcrystalline Cellulose that obtains.
This experimental result shows, in the situation that do not add acid in 165 ℃ of lower hydrolysis 180 minutes, is the even crystallite Mierocrystalline cellulose of the better quality of approximately 20 μ m in the situation that obtain median size without any mechanical treatment.
Embodiment 2
With above-mentioned experiment processes employ in the paper pulp of full bleaching.The concentration of hydrolysis stage is 15%, and boiling temperature is 150 ℃, and cooking time is 120 minutes.The size distribution that in Fig. 2, has shown the Microcrystalline Cellulose that obtains.
This experimental result shows, in the situation that do not add acid in 150 ℃ of lower hydrolysis 120 minutes, is the even crystallite Mierocrystalline cellulose of the suitable better quality of approximately 50 μ m in the situation that obtain median size without any mechanical treatment.Compare with embodiment 1, particle diameter is larger a little.
Claims (14)
1. method of producing Microcrystalline Cellulose, the method comprises:
A) with the fibrous cellulosic materials acidifying,
B) wash the cellulose materials of this acidifying,
C) the cellulose materials dehydration that randomly will wash, and
D) with at least 120 ℃ temperature with at least 8% concentration of pressing the Mierocrystalline cellulose dry weight basis, under acidic conditions, make the cellulosic material hydrolysis of this washing or washing and dehydration.
2. according to claim 1 method, wherein described cellulose materials is acidified to 4 or be lower than 4, preferred 3 or be lower than 3, the more preferably pH value of 1.5-2.5.
3. according to claim 1 and 2 method is wherein used mineral acid, and preferably sulfuric acid, hydrochloric acid, nitric acid, sodium pyrosulfate or sodium pyrosulfate are with described fibrous cellulosic materials acidifying.
4. each method according to claim 1-3, wherein the temperature in the acidification step is preferably 10-90 ℃ less than 120 ℃, more preferably 20-70 ℃.
5. each method according to claim 1-4, wherein acidificatoin time is 10-90 minute, preferred 15-60 minute.
6. each method according to claim 1-5 is wherein utilized the own acidity of described cellulose materials in hydrolysis.
7. each method according to claim 1-6, wherein the temperature in the steps d is 120-185 ℃, preferred 150-180 ℃, more preferably 155-175 ℃.
8. each method according to claim 1-7, wherein the concentration of cellulose materials described in the steps d is counted 8-60% with the Mierocrystalline cellulose dry weight, preferred 10-50%, more preferably 15-50%, most preferably 20-45%.
9. each method according to claim 1-8, wherein hydrolysis time is 20-300 minute, preferred 30-240 minute, more preferably 60-240 minute.
10. each method according to claim 1-9, wherein said fibrous cellulosic materials derives from the xylophyta material, for example soft wood or hardwood.
11. each method according to claim 1-10, wherein said fibrous cellulosic materials comprises bleaching or unbleached dissolving pulp, for example sulfate pulping, soda-AQ paper pulp, sulfite pulp, neutral sulfite pulp, acid accumulator sulfite paper pulp or organic solvent paper pulp.
12. each method according to claim 1-11, wherein said fibrous cellulosic materials derives from nonwood plant materials, for example the stalk of cotton, grass, bagasse, cereal crop, flax, hemp, sisal hemp, abaca or bamboo.
13. each method according to claim 1-12, wherein said fibrous cellulosic materials for example dissolving pulp have and are lower than 40 Kappa numbers, preferably are lower than 30 Kappa numbers, more preferably less than the content of lignin of 10 Kappa numbers.
14. each method according to claim 1-13, the Microcrystalline Cellulose of wherein producing has the median size of 10-60 μ m, and preferably size distribution so that the particle of at least 90 volume % has the size that is lower than 250 μ m.
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FI20105639A FI123270B2 (en) | 2010-06-07 | 2010-06-07 | Manufacturing of microcellulose |
PCT/FI2011/050523 WO2011154597A1 (en) | 2010-06-07 | 2011-06-06 | Manufacturing of microcellulose |
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Cited By (3)
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CN106519173A (en) * | 2016-11-29 | 2017-03-22 | 桂林理工大学 | Method for preparing shape memory polyurethane from hyperbranched modified sisal microcrystals |
CN107936125A (en) * | 2017-12-11 | 2018-04-20 | 厦门大学 | A kind of preparation method of micro-nano cellulose |
CN111019154A (en) * | 2019-12-30 | 2020-04-17 | 上海昶法新材料有限公司 | Method for extracting lignin and microcrystalline cellulose from chemi-mechanical pulp treatment waste liquid |
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RU2505545C1 (en) * | 2012-07-31 | 2014-01-27 | Закрытое акционерное общество "Инновационный центр "Бирюч" (ЗАО "ИЦ "Бирюч") | Method for obtaining nano-cellulose |
CN102911274B (en) * | 2012-10-17 | 2014-05-28 | 浙江理工大学 | Method for chemically preparing nano microcrystalline cellulose by utilizing moso bamboo |
SE1350057A1 (en) * | 2013-01-18 | 2014-07-19 | Process for manufacturing microfibrillated cellulose from a precursor material | |
FI129421B (en) * | 2014-03-12 | 2022-02-15 | Maelkki Yrjoe | Production and use of nanocellulose and its precursors |
CN107532379B (en) * | 2015-05-14 | 2020-12-22 | 杜邦营养美国有限公司 | Process for producing bleached microcrystalline cellulose |
FI130254B (en) * | 2016-02-03 | 2023-05-11 | Kemira Oyj | A process for producing microfibrillated cellulose and a product thereof |
US10287366B2 (en) | 2017-02-15 | 2019-05-14 | Cp Kelco Aps | Methods of producing activated pectin-containing biomass compositions |
BG67355B1 (en) * | 2017-11-17 | 2021-07-15 | Свилоза - Ад | Method for preparing microcrystalline cellulose |
FI129209B (en) * | 2018-02-07 | 2021-09-15 | Andritz Oy | Process for producing microcrystalline cellulose |
RU2684082C1 (en) * | 2018-04-11 | 2019-04-03 | Общество С Ограниченной Ответственностью "Национальная Исследовательская Компания" | Method for producing microcrystalline cellulose |
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CA2801986A1 (en) | 2011-12-15 |
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CN102947343B (en) | 2016-03-30 |
FI20105639A (en) | 2011-12-08 |
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PL2576627T3 (en) | 2019-01-31 |
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BR112012031247B1 (en) | 2020-05-26 |
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UY33436A (en) | 2011-12-30 |
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